Hydrocarbon conversion process with gd catalyst



United States Patent Ofice 3,541,001 Patented Nov. 17, 1970 U.S. Cl.208-135 9 Claims ABSTRACT OF THE DISCLOSURE A process for convertinghydrocarbons comprises contacting a hydrocarbonaceous feed in aconversion zone at an elevated temperature with a Gb alumino-silicatezeolite catalyst and recovering an upgraded hydrocarbon conversionproduct. The process can involve double-bond isomerization,hydroisomerization, cracking, hydrocracking, cyclization, reforming anddealkylation.

The zeolite can be amorphous but preferably is at least partiallycrystalline and can adsorb benzene. The zeolite, in the hydratedcondition, is chemically characterized by the empirical formula M (AlO(SiO (H O) where x, y and z are integers, the ratio x-zy being usuallyfrom 1.0 to 0.2 and where at least 25% (and preferably more than 40%) ofthe negative charge associated with the aluminum of the alumino-silicateframework is satisfied by a cation of Gd or a cation of an oixde or ahydroxide of Gd. Preferably, upon ignition analysis the catalyst willevolve from 0.25 to 6 molecules of water for each atom of Gd in thecatalyst.

The zeolite can contain additional cations of polyvalent metals,preferably cations containing magnesium, aluminum, silver, nickel, zinc,cerium or lanthanum. In such catalysts it is preferred that at least onesuch cation be present for every 20 atoms of aluminum in thealuminosilicate framework for the zeolite.

For hydrocracking, reforming and hydroisomerization the Gd catalyst iscombined with a hydrogenation catalyst, such as nickel, cobalt,palladium, ruthenium, rhodium, rhenium or platinum.

For the hydroisomerization of petroleum refinery streams which containat least 20% of C C normal paraflin, the preferred catalyst combinationcontains from 0.1 to 2 weight percent of platinum, rhenium or palladiumor from 1 to 10% of nickel.

CROSS REFERENCES TO RELATED APPLICATIONS Gd-containing zeolites whichcan be utilized as catalysts in the subject process have been describedin copending application Ser. No. 590,225 filed Oct. 28, 1966 of RonaldD. Bushick entitled Alumino-Silicate Catalyzed Reactions of PolycyclicAromatic Hydrocarbons, now Pat. No. 3,396,203 and in copendingapplication Ser. No. 581,129, filed Aug. 25, 1966 of Francis WilliamKirsch, David S. Barmby and John D. Potts entitled Process for Paraffin-Olefin Alkylation, now abandoned and in copending application, Ser. No.716,190, filed of even date with the present application, of FrancisWilliam Kirsch, David S. Barmby and John D. Potts entitled Process forParaffin-Olefin Alkylation, and in copending application Ser. No.718,980, filed of even date with the present application, of Ronald D.Bushick entitled Combination of Gd Alumino-Silicate Catalyst andHydrogenation Catalyst, and in copending application Ser. No. 715,998,filed of even date with the present application of Francis WilliamKirsch, David S. Barmby and John D. Potts entitled Gd Zeolite andHydrocarbon Conversion Process with Gd Zeolite Catalyst, all of thesebeing assigned to the Sun Oil Company. The disclosure of all of theabove-cited applications is hereby incorporated in the presentapplication.

BACKGROUND OF THE INVENTION Although it is known to utilize crystallinealu'mino-silicate zeolites containing cations of lanthanum, cerium or ofcertain rare earth salt mixtures as hydrocarbon conversion catalysts(e.g., see US. 3,140,249 and US. 3,210,- 267 the art has failed torealize that incorporation of substantial quantities of gadoliniumcations in an amorphous or crystalline alumino-silicate zeolite can beused to produce an adsorbant for aromatic hydrocarbons or a catalystwhich is especially useful for hydrocarobn conversion reactions, andparticularly conversions involving carbonium-ion mechanisms. Similarly,the art has failed to appreciate that a combination of a Gdalumino-silicate catalyst with a hydrogenation catalyst can beespecially useful for conversions involving catalytic contacting ofhydrocarbons in the presence of hydrogen, such as aromatization ofnaphthenes or olefins, cyclizations, reforming, hydrocraeking andhydroisomerization.

BRIEF SUMMARY OF THE INVENTION Hydrocarbon conversion reactions, such ascracking, dehydrogenation, reforming, alkylation, dealkylation,cyclization and isomerization can be effected by contacting ahydrocarbon feed with a catalyst comprising an alumino-silicate zeolitecontaining cations of gadolinium, such as Gd+ Gd(OH)+ and Gd(OH) Alsoeffective as catalysts in such processes are novel catalysts comprisinggadolinium-containing zeolites which also contain magnesium cations,aluminum cations, silver cations, nickel cations, zinc cations, ceriumcations, lanthanum cations, cations of the hydroxides or oxides of thesemetals or mixtures of two or more of such cations.

The preferred zeolite catalyst is crystalline and capable of adsorbingbenzene, has an atomic ratio Al/ Si of 0.65 to 0.35 and contains atleast one Gd(OH) cation for every 8 atoms of aluminum in thealumino-silicate framework. The zeolite can also be utilized as anadsorbant, as for separating aromatic hydrocarbons from less polarcompounds. In conversions involving oxidative regeneration of thiscatalyst (or adsorbant), crystallinity can decrease, usually accompaniedby a decrease in activity and/ or selectivity. The resulting, moreamorphous, zeolite can be eifective as a catalyst, particularly atconversion temperatures which are greater than those required for thecorresponding conversion with an equal weight of crystalline zeolite.

An especially useful hydrocarbon conversion reaction is thehydroisomerization of the C -C paraffin hydrocarbons which are capableof conversion to more highly branched isomers, in order to obtain a morehighly branched product with improved octane ratings. Another especiallyuseful conversion is the alkylation of (I -C aromatic (or C7c22 alkylaromatic) hydrocarbons, or C -C paraflin hydrocarbons, with olefinhydrocarbons. Another especially useful conversion is the isomerizationof such polycyclic aromatic hydrocarbons as s-octahydrophenanthrene(s-OPH) to produce s-octahydroanthracene (s-OHA) and/or such aromatichydrocarbons as l-cyclohexyl-Z- phenyl ethane, asymmetricaloctahydrophenanthrene, 1,2, 3,4-tetrahydroanthracene,l,2,3,4-tetrahydrophenanthrene, anthracene, phenanthrene, and tetralin.

FURTHER DESCRIPTION OF THE INVENTION Pentene-isomerization activity is ameasure of the acid activity of a catalyst, and, therefore, indicativeof the ability of the catalyst to catalyze typical carbonium-ionreactions such as cracking, dealkylation, aromatic alkylation,polymerization, isomerization, etc. By utilizing the isomerization ofpentene-l as a test reaction, it has been found that a substantiallyanhydrous GdHY catalyst, prepared by activation of a crystalline GdNH Yzeolite (obtained by Gd-cation exchange of highly ammonium-exchangedsodium Y zeolite), is more effective than a similarly prepared CeHYcatalyst wherein, instead of aqueous gadolinium cations, aqueous ceriumcations were present in the exchange medium.

In the Gd alumino-silicate catalyst, at least 25% and, preferably, atleast 40% of the electronegativity associated with the alumino-silicateframewonk is satisfied by cations of gadolinium or of its oxides orhydroxides. When the Gd catalyst contains less than one alkali metalcation (e.g. Na+) for every 4 aluminum atoms in the aluminosilicateframework, the catalyst is especially useful for such hydrocarbonconversion reactions as isomerizing polycyclic aromatic hydrocarbons,paraffin-olefin alkylation and the cracking of gas oil. Preferably, thealuminosilicate zeolite is crystalline and is chemically characterizedby the empirical Formula M (AlO '(SiO -(H O) where x, y and z areintegers, the ratio x/ y being from 1.0 to 0.2 and where M is chosenfrom at least one of the following groups:

(1) at least one Gd+ cation for every 12 atoms of aluminum in thealumino-silicate framework of said zeolite;

(2) at least one cation of Gd(OH)+ for every 8 atoms of aluminum in thealumino-silicate framework of said zeolite;

(3) at least one cation of Gd(CH). for every 4 atoms of aluminum in thealumino-silicate framework of said zeolite;

(4) a combination of the members of at least two of the above groups;

and wherein the balance of the cations necessary for electronicequivalency comprises H+ or cations of metals, metal oxides or metalhydroxides and wherein there is less than one alkali metal cation forevery four atoms of aluminum in the alumino-silicate zeolite, morepreferably, less than one alkali metal cation for every ten atoms ofaluminum.

The Gd zeolite can contain as such additional cations, the cations ofmagnesium, aluminum, silver, nickel, zinc, cerium, lanthanum andmixtures of these cations. In such catalysts it is preferred that atleast one such cation is present for every 20 atoms of aluminum in thealuminosilicate framework of said zeolite.

For most hydrocarbon conversions, the ratio x/z in the empirical formulaof the zeolite should be in the range of 0.25 to 2. If excess water ispresent, the zeolite should be activated by heating according to theprocedure disclosed in the aforementioned applications of Kirsch, Barmbyand Potts. If the zeolite is deficient in bound water, water can beadded, as by exposure to steam in air or nitrogen.

As used herein, the term framework, in reference to the alumino-silicateportion of the zeolite (which can be crystalline or amorphous), excludesthose aluminum ions which are in exchange positions and which areneutralizing some of the negative charge associated with the aluminumatoms in the alumino-silicate tetrahedra of the zeolite. Note thataluminum in the alumino-silicate framework can be either trigonal ortetrahedral.

For such reactions as reforming, aromatization, hydrogen transfer,hydrocracking and hydroisomerization, it is preferred that the catalysthave incorporated therewith from 0.05 to 25% (more preferably, 0.05 to5%) of a hydrogenation catalyst component containing a hydrogenactivemetal such as platinum, palladium, rhodium, rhenium, ruthenium,molybdenum, cobalt or nickel (or a chemical compound, as an oxide orsulfide, of such a metal). The hydrogen-active metal can also beincorporated on a carrier (as alpha-alumina, microporous silica,conventional amorphous silica-alumina cracking catalyst, oracid-exchanged clays, such as montmorillonites or kaolin). When thehydrogen-active metal component (or a chemical compound of the metal) isso incorporated on a carrier, it is preferred that the Gd catalyst bephysically admixed therewith.

When the hydrocarbon conversion involves cyclization and/oraromatization, as with a feed of n-pentene, nhexene, n-heptene or1,4-dimethylnaphthalene, the cyclization conditions comprise atemperature in the range of 350-850 F. and a pressure in the range of0-750 p.s.i.g., preferably with the reactants maintained in the vapor ortrickle phase. For aromatization and/or cyclization of a crackednaphtha, temperature in the range of 240 600 F. is preferred atatmospheric pressure. For a hydrogen transfer reaction, to producearomatics from naphthenes, a temperature in the range of 300-500 F. atatmospheric pressure is preferred, as when cyclohexane and propylene arethe feed hydrocarbons and the products are benzene plus propane.

For double-bond isomerization, such as for the conversion ofZ-ethyl-l-butene to cis and trans 3-methyl-2-pentene, or the conversionof pentene-l to pentene-Z, a temperature in the range of 70-400 F. andpressures from 0-75 p.s.i.g. are preferred, with the lower temperaturesand higher pressures most preferred in order to reduce cracking.

For isomerization and/or transalkylation of alkyl benzenes, such asconverting meta-xylene to ortho the para xylene, the hydrocarbonreactant can be either in liquid or vapor phase at a temperature in therange above about 60 C. and below cracking temperature. The preferredtemperature range for xylene isomerization is -350 C. and preferably inthe presence of added hydrogen (e.g. 575 p.s.i.).

When the primary conversion reaction is cracking, -a temperature in therange of 800-1100" F. is preferred for a gas oil feed, preferably atatmospheric or slightly elevated pressure, although pressures as low as1 mm. Hg and as high as 1200 p.s.i.g. can be utilized in such crackingreactions. When the predominant reaction is hydrocracking, our preferredhydrogen-active metal is selected from Group VI-b, and more preferablycomprises Ni, Pd or Pt. The preferred hydrogen pressure is in the rangeof 500-5000 p.s.i. at conversion temperatures from 650- 1100 F.

For paraffin-olefin alkylation, the preferred process conditions with aC -C feed olefin are those of the aforementioned patent applications ofKirsch, Barmby and Potts. Generally, these involve (a) contacting C -Cmonoolefin with C -C isoparafiin and with a substantially anhydrous Gdzeolite catalyst at a temperature below the critical temperature of thelowest boiling hydrocarbon reactant and at a pressure such that each ofthe reactants is in liquid phase, and,

(b) stopping such contacting after substantial alkylation has occurredbut before the weight rate of production of unsaturated hydrocarbonbecomes greater than the weight rate of production of saturatedhydrocarbon.

Preferably, the feed olefin and feed paraffin are admixed prior tocontact with the catalyst and the concentration of unreacted olefin iskept sufiiciently low that predominantly saturated par-affin-olefinalkylation products are obtained rather than unsaturated products. Thisconcentration is preferably less than seven, more preferably less than12 mole percent, based on the total parafiin content of the reactionmixture. Also preferred is the use of a halide adjuvant (as HCl, CCl andthe C -C monochloro paraffins) containing bromine, chlorine or fluorine,to increase the yield of liquid paraffin based on the olefin charged.Also preferred is a temperature in the range of 25120 C. and a meanresidence time of the reaction mixture with the catalyst in the range of0.05 to 0.5 hours per (gram of catalyst per gram of hydrocarbon in thereaction mixture). When the feed olefin comprises ethylene, conditionsshown 5 in U.S. 3,251,902 can be used to produce a liquid product;however, this liquid product is generally less preferred as a componentof gasoline than are the highly branched liquid paraflin hydrocarbonswhich are produced by the aforementioned process of the Kirsch, Barm byand =Potts applications.

For the isomerization of such polycyclic aromatic hydrocarbons as s-OHAto its isomer s-OHP, or s-OHP to its isomer s-OHA, the preferredconditions include a tem .perature above 80 C. and below crackingtemperature and are shown in the aforementioned application of Ronald D.Bushick, Ser. No. 590,225. This Bushick application also shows thepreparation of a novel composition comprising an acidic Gdalumino-silicate catalyst and from 0.5 to 5% of a hydrogenationcatalyst. Preferably the hydrogenation catalyst is selected from thegroup consisting of platinum, palladium, nickel, nickel oxide, nickelsulfide, molybdenum oxide, molybdenum sulfide, cobalt oxide, palladiumoxide and mixtures thereof. The hydrogenation catalyst can be physicallyadmixed with the acidic alumino-sil-icate, or have been incorporatedinto the alumino-silicate by salt impregnation or by ion exchange. Whenthe salt has been introduced into the alumino-silioate catalyst by ionexchange, it is preferred that the hydrogenation catalyst be reduced, aswith hydrogen, prior to contact of the catalyst with the hydrocarbonfeed. Also preferred is a process for the isomerization of polycyclicaromatic hydrocarbons, such as s-OHA or s-OHP, wherein the Gdcatalyst/hydrogenation catalyst combination and from 25-1000 p.s.i.g. ofhydrogen are present in the re actor. The added hydrogen aids inmaintaining the activity of the isomerization catalyst combination, andcan be recycled at rates up to 10,000 s.c.f./bbl. of feed. The LHSV ispreferably in the range of 0.25-5 .0 volumes of feed per volume ofcatalyst per hour.

In any of the above-listed reactions, if the catalyst activityappreciably decreases during the course of the reaction, the catalystmay be separated from the hydrocarbon reactants and regenerated, as byburning in air. After such burning, water can be added to the catalyst,as by exposure to steam in air or nitrogen. When a hydrogenactive metalis incorporated into the zeolite catalyst, it is sometimes advantageousto reduce the regenerated combination with hydrogen, preferably at 250to 800 F., prior to introduction of the hydrocarbonaceous feed.

When the primary hydrocarbon conversion is a hydroisomerization or areforming reaction, the preferred con ditions include a hydrogenpressure of at least 25 p.s.i.g. and temperatures from 500 to 700 F.,although the conversion can be effected in the range of 225-1000 F., attotal pressures in the range of 0 5000 p.s.i.g. and hydrogen pressuresin the range of 0.5-4000 p.s.i.g. For the hydroisomerization of C -Cparaflins, the preferred catalyst combination will contain from 0.1 to 2percent of Pt, Pd or Re (or a mixture thereof) or from 1 to 10% of Ni.

Typical feeds and reaction conditions which are effective when utilizingthe Gd catalyst, particularly when combined with a hydrogenationcatalyst, for hydroisomerizat-ion or reforming are those in thefollowing U.S. Pats: 2,834,439; 2,970,968; 2,971,904; 2,983,670;3,114,695; 3,122,494; 3,132,089; 3,140,253; 3,146,297; 3,190,939;3,197,398; 3,201,356; and 3,236,762.

In processes utilizing the Gd catalyst, whether alone or in combinationwith a hydrogenation catalyst, halide adjuvants containing chlorine,fluorine or bromine can frequently be used to increase the degree ofconversion. Preferred adjuvants include C01 HCl, A1Br BF HF and the C -Cchlorohydrocarbons.

ILLUSTRATIVE EXAMPLES In the following examples, Example I shows thepreparation of a preferred embodiment of the Gd catalyst and Example IIshows the incorporation therewith of a Pthydrogenation catalyst. Example111 shows contacting n-pentane .with this combination of a Gd catalystand a Pt catalyst and obtaining, as the major product, isopentane.Example IV shows a similar hydrocarbon conversion of n-pentane, whereinExample III is repeated except that a CeHY zeolite is substituted forGdHY zeolite in the catalyst combination. Example V shows a testreaction with a pentene-l feed which indicates that the Gd zeolitecatalyst of Example I has appreciably greater activity than a similar Cezeolite catalyst for carbonium-ion reactions such as cracking (includinggas oil cracking), Example VI shows the hydroisomerization of a straightrun gasoline stream, by contacting with the Gd catalyst/ hydrogenationcatalyst combination of Example II, to upgrade the octane rating of thegasoline. Example VII shows paraffin-olefin alkylation with the Gdzeolite catalyst of Example I.

EXAMPLE I About 500 g. of NaY zeolite was exchanged, filtered and washedfor 16 cycles with aqueous NH Cl utilizing the procedures disclosed inthe aforementioned U.S. application, Ser. No. 581,129. The resulting NHY zeolite Was similarly exchanged for 16 cycles with aqueous gadoliniumnitrate. The resulting Gd-exchanged NH exchanged zeolite was washed freeof nitrate and unexchanged gadolinium ions, with distilled water, anddried in an oven at about to produce a GdNH Y zeolite. The zeolite wasactivated by heating slowly to 400 C. to remove water and decompose thebulk of any remaining ammonium ions. This activation utilized theprocedures disclosed in the aforementioned U.S. Ser. No. 581,129. Thezeolite before activation had the analysis listed in the attached Table2 under the heading Run No. 628 (Run No. 674 is also this zeolite). Theresulting substantially anhydrous GdHY zeolite was crystalline andcapable of adsorbing benzene. The Weight loss upon ignition analysis at1800 C., of the activated zeolite was 3.41%.

EXAMPLE n A solution of Pt(NH Cl in water was added dropwise withstirring to a dilute aqueous suspension of the catalyst in water, at 55C. The amount of Pt(NH Cl used was equivalent to 0.5% Pt in theactivated catalyst. After the Pt salt addition was complete (about 1hr.), the solution was stirred at 55 C. for 30 minutes, filtered, andthe catalyst washed' with distilled water until the washings were freeof chloride ion. The catalyst was dried, heated to 400 C. in a stream ofdry air and then reduced at 400 C. in the reactor in a flowing stream ofH for one hour.

EXAMPLE III were products having a molecular weight higher thann-pentane.

EXAMPLE IV Example II was repeated except that the catalyst combinationwas a similarly activated combination of an activated cerium-exchanged,ammonium-exchanged Y zeolite and 0.5% of Pt. The reaction productcontained only 51.7% of isopentane. That is, the Gd zeolite catalystcombination produced nearly 8% more isopentane than did the Ce zeolitecatalyst combination.

EXAMPLE v A 4.2 ml. portion of a solution of 21% pentene-l in n-pentanewas shaken with 0.50 g. of each above catalyst. Portions of the liquidwere removed periodically for analysis. After 7 minutes contact time theconversion to pentene-2 was 12.7% over the Ce-HY and 72.8% over theGdHY. The monomeric olefin concentrations in the liquid phase were 17.3%and 12.5% respectively, showing that the GdHY was more active forpolymerization of the olefin as well as for the isomerization topentene-2.

EXAMPLE VI A straight run gasoline feed was contacted at 325 C., 400p.s.i.g. total pressure, in a tubular reactor, in the presence of added100% hydrogen, with a bed of the reduced catalyst combination of ExampleII. Table I, under the heading GdHY-90.5% Pt reports the analysis andcalculated octane ratings of the product obtained from three such runs,at various space rates and hydrogen/ hydrocarbon ratios. These dataindicate that preferred conditions for such gasoline upgrading (ofstreams containing at least 25% C -C normal paraflin) with a Gdzeolite-hydrogenation catalyst combination (at 300-340 C.) include anLHSV of l to 4 (more preferably 1.5 to 2.5) at a hydrogen to hydrocarbonmolar ratio in the range of 1 to 6.

TABLE 1.ISOMERIZATION OF 0 -06 GASOLINE FOR 00- TANE UPGRADING ALL RUNSAT 325 C. AND 400 P.S.I.G.

Product GdHY+0.5% Pt Hydrocarbon, wt. percent Feed A 1 B 2 0 Ca 0. 6 0.6 0. 8 i-C 0.3 2.4 1. 9 2.3 n-C4 4.6 4. 2 4. 2 4. i i-C5 18.7 35. 2 33.2 31. I 11-05---" 35. 8 22. 4 21. 5 21. 7 2,2-DMB 1.1 4. 4 5. 5 5. 5Cycle 05 3. 5 3. 0 3.0 3.0 2,3-DMB 2. 2 2. 7 3. 0 3. 0 2-MP 13. 6 10.411.3 11. 4 3-MP- 6.1 7.2 7.7 7.8 n-Cu 9. 4 6. 5 7. 0 7. 0 C 1. 7 0. 9 1.0 0. 9 Cyclohexane. 0. 2 0. 1 0. 1 0. 1 Benzene 0. 7 Heptanes 0. 5 TraceTrace Trace Octanes 1. 2 Percent iso C in C5 34. 4 61 60. 6 59. 5Percent iso C6 in Ca 71 79.2 79. 7 79.8 Percent 2,2-DMB in Ca. 3. 4 l4.1 15. 9 15. 9 Calculated:

F-l clear 70. 6 79. l 78. 8 77. 5 IT-1+3 cc 88. 6 94. 0 94. 7 93. 0

1 Run A at 1.6 LHSV and 2.1 Hz/HC. 2 Run B at 0.8 LHSV and 3.7 Hz/HC. 3Run 0 at 0.8 LHSV and 3.1 Hz/HC.

H /HC=molar ratio hydrogen/hydrocarbon LHSV=liquid hourly space velocityin volume of feed per volume of catalyst per hour All catalystsconditioned 48 hours at 325 C./400 p.s.i.g., 3 LHSV with n-pentane priorto contact with the straight run gasoline.

EXAMPLE VII This example illustrates the use of substantially anhydrousacidic crystalline Gd alumino-silicate zeolite as a paraffin-olefinalkylation catalyst. The catalyst of Example I (prepared by activating a16-cycle Gd+ /16-cyc1e NHJ-exchanged Type Y zeolite) was charged inamount of 23.3 g. into a one-liter, stirred autoclave containing afour-member baffle to diminish vortex formation. Then 444 milliliters ofliquid isobutane and 1.0 g. of tertiary butyl chloride was added. Thestirring rate (of a sixmember, flat-blade turbine) was adjusted suchthat substantially all of the zeolite was suspended in the liquidisobutane (about 550 r.p.m.). The temperature in the reactor was raisedto C. using sufficient nitrogen to produce a total pressure of 250p.s.i.g. Under these conditions, nearly all of the hydrocarbon is in theliquid phase. Then a liquid mixture of one part by volume of butene-2and five volumes of isobutane was charged from a Jerguson gauge via aneedle valve and dip tube into the isobutane-catalyst slurry (and nearthe bottom of the reactor) at the rate of one milliliter of mixture perminute for a period of 220 minutes. Nearly all of the hydrocarbon wasmaintained in liquid phase. At the end of this time the reaction wasstopped by cooling the reactor to 17 C., then separating the reactionmixture from the catalyst by first removing the normally gaseoushydrocarbons at room temperature and atmospheric pressure, and thenseparating the liquid product from the catalyst by filtration. Somepropane and n-butane but no methane, ethane, ethylene or propylene werefound in the normally gaseous hydrocarbons. Table 2 reports thecomposition of the C liquid product of this reaction (Run 628) and of asimilar reaction run with a catalyst prepared firom the same zeolite butby activation is helium rather than in air (Run 674). Also shown aresimilar runs made with catalysts prepared by air activation of a highlyammonium-exchanged Type Y zeolite (Run 576), a zeolite prepared as inExample I but exchanged with aqueous cerium nitrate instead of theaqueous gadolinium nitrate (Run 642) and a zeolite prepared by suchcerium exchange of a highly ammonium-exchanged Type X zeolite (Run 622).

TABLE 2.LIQUID PHASE ISOPARAFFIN-OLEFIN ALKYLATION WITH SOLID ZEOLITECATALYSTS [Gadolinium versus Ammonium versus Cerium and Type X versusType Y Zeolite. Autcgenous pressure 80 0., i-C -ane/C ene-2=15 (min),3.67 hr., 1.0 g. tertiary butyl chloride adjuvant] Catalyst:

Zeolite before activatiom Activation (400 0.) gas.

05+ paraflln yield, wt. percent 00.

0 unsaturates, Wt. percent 00 0.00

0 parafiin distribution, mole percent:

2,3 3- Catalyst Analysis (ignited basis, before activa- Wt. percent NaWt. percent Ce or G Wt. percent N Wt. percent loss on ignition TABLE2Continued Analysis of Base Na zeolite (before exchange,

ignited basis):

*Base CeNH X zeolite analyzed 37.56% S102 (17.56% Si).

I claim:

1. A hydrocarbon conversion process comprising hydroisomerizing afeedstock consisting essentially of C to C paraflin hydrocarbons at anelevated conversion temperature with a Gd alumino-silicate zeolitecatalyst and recovering an upgraded hydrocarbon conversion product, andwherein said Gd alumino-silicate zeolite is crystalline and ischemically characterized by the empirical formula M (A1O (SiO (H O)where x, y and z are integers, the ratio xzy being from 0.65 to 0.2 andwhere M is chosen from at least one of the following groups:

(a) at least one Gd+ cation for every 12 atoms of aluminum in thealumino-silicate framework of said zeolite;

(b) at least one cation of Gd(OH) for every eight atoms of aluminum inthe alumino-silicate framework of said zeolite;

(c) at least one cation of Gd(OH) for every four atoms of aluminum inthe alumino-silicate framework of said zeolite; or

(d) a combination of the members of at least two of the above groups;

and wherein the balance of the cations necessary for electronicequivalency comprise H+ or cations of metals, metal oxides or metalhydroxides and wherein there is less than one alkali metal cation forevery four atoms of aluminum in the alumino-silicate zeolite.

2. Process according to claim 1 wherein said catalyst contains from 0.05to by weight of a hydrogenation catalyst.

3. Process according to claim 2 wherein said zeolite is at leastpartially crystalline and is capable of adsorbing benzene and whereinsaid hydrogenation catalyst contains at least one member of the groupconsisting of nickel, cobalt, palladium, ruthenium, rhodium, rhenium andplatinum.

4. Process according to claim 3 wherein the atomic ratio Al/Si of thealumino-silicate framework of the crystalline portion of said zeolite isfrom 0.65 to 0.35.

5. Process according to claim 3 wherein said Gd alumino-silicate zeolitecatalyst, upon ignition analysis at 1800 F., evolves from 0.25 to 6molecules of water for each atom of Gd in said catalyst.

6. Process according to claim 3 wherein at least 40% of the negativeelectrical charge associated with the aluminosilicate framework issatisfied by at least one cation from the group consisting of Gd+ Gd(OH)and Gd(OH) 7. Process according to claim 3 wherein saidhydrocarbonaceous feed is a petroleum refinery stream which contains atleast 20% of C -C normal parafiin and wherein there is recovered ahydrocarbon conversion product having an increased octane rating.

8. Process according to claim 7 wherein said catalyst contains from 0.1to 2 weight percent of platinum, rhenium or palladium or from 1 to 10%of nickel.

9. Process according to claim 8 wherein the atomic ratio Al/Si of thealumino-silicate framework of the crystalline portion of said zeolite isabout 0.4.

References Cited UNITED STATES PATENTS 3,140,253 7/1964 Plank et al 2083,173,855 3/1965 Miale et al. 208120 3,247,099 4/1966 Oleck et a1.208-138 3,251,902 5/1966 Garwood et a1. 260683.64 3,301,917 1/1967 Wiseet al 260683.65

HERBERT LEVINE, Primary Examiner U.S. Cl. X.R.

